Heterometallic Trinuclear Polyhydrido Complexes Containing Ruthenium and a Group 9 Metal, [CP*3Ru2M(mu(3)-H)(mu-H)(3)] (M = Ir or Rh; Cp* = eta(5)-C5Me5): Synthesis, Structure, and Site Selectivity in Reactions with Phosphines

Shima T; Sugimura Y; Suzuki H

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Heterometallic Trinuclear Polyhydrido Complexes Containing Ruthenium and a Group 9 Metal, [CP3Ru2M(mu(3)-H)(mu-H)(3)] (M = Ir or Rh; Cp = eta(5)-C5Me5): Synthesis, Structure, and Site Selectivity in Reactions with Phosphines

机译：含有钌和9族金属[CP * 3Ru2M（mu（3）-H）（mu-H）（3）]的杂金属三核多氢配合物（M = Ir或Rh; Cp * = eta（5）-C5Me5）：与膦反应的合成，结构和位点选择性

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A heterometallic trinuclear polyhydrido complex, [Cp*3Ru2Ir(mu(3)-H)(mu-H)(3)] (CP* = eta(5)'-C5Me5) (1), was synthesized by dehydrogenative coupling between a dinuclear ruthenium tetrahydrido complex, [Cp*Ru(mu-H)(4)RuCp*], and an equimolar amount of a mononuclear iridium tetrahydrido complex, Cp*IrH4. The Ru-Rh analogue, [Cp*3Ru2Rh(mu(3)-H)(mu-H)(3)] (2), was synthesized by reacting a 2:1 mixture of the dichlorido dimers (Cp*RuCl2)(2) and (Cp*RhCl2)(2) with NaBH4. The molecular structure of [CP*(2)(C5Me4Et)Ru-2-Ir(mu(3)-H)(mu-H)(3)] (1 '') was determined through single-crystal X-ray diffraction. The mutual exchange of the hydrido ligands in 1 among the coordination sites was analyzed using variable-temperature (VT)-H-1 NMR spectroscopy. Complex 1 undergoes an H/D exchange between the hydrido ligands and C6D6 via C-H bond cleavage/formation. The reactivity of 1 toward tertiary and secondary phosphines was studied to elucidate the roles of each metal atom in the substrate activation step. The reactions of 1 with tertiary phosphines afford the phosphine complexes [Cp*3Ru2Ir(PR3)(mu-H)(4)] (R = Me, 3a; Et, 3b; Ph, 3c; OMe, 3d), in which the phosphine is bound to the one of the Ru atoms in a terminal mode. Treatment of 1 with PPh2H exclusively produces a mu-phosphido complex, [CP*3Ru2Ir(mu-PPh2)(mu-H)(3)] (5), in which the phosphido ligand bridges the Ru-Ir edge through the intermediary mu-phosphido complex [CP*3Ru2Ir(mu-PPh2)(mu-H)(5)] (6), in which the phosphido ligand bridges the Ru-Ru edge. The fluxional behavior of the mu-phosphido ligand in 5 was elucidated by VT-H-1 NMR and selective pulse irradiation. Thermolysis of 5 generates a mu(3)-phosphinidene complex, [Cp*3Ru2Ir(mu(3)-PPh)(mu-H)(2)] (7), via P-C(ipso) bond cleavage and the reductive elimination of benzene.

机译：杂金属三核多氢络合物[Cp * 3Ru2Ir（mu（3）-H）（mu-H）（3）]（CP * = eta（5）'-C5Me5）（1）通过在双核钌四氢配合物[Cp * Ru（mu-H）（4）RuCp *]和等摩尔量的单核铱四氢钌配合物Cp * IrH4。 Ru-Rh类似物[Cp * 3Ru2Rh（mu（3）-H）（mu-H）（3）]（2）是通过使二氯二聚体（Cp * RuCl2）的2：1混合物反应合成的（ 2）和（Cp * RhCl2）（2）和NaBH4。通过单晶X射线衍射确定[CP *（2）（C5Me4Et）Ru-2-Ir（mu（3）-H）（mu-H）（3）]（1）的分子结构。使用可变温度（VT）-H-1 NMR光谱分析了配位点之间1中的氢配体的相互交换。配合物1通过C-H键裂解/形成在氢化配体和C6D6之间进行H / D交换。研究了1对叔膦和仲膦的反应性，以阐明每个金属原子在底物活化步骤中的作用。 1与叔膦的反应得到膦络合物[Cp * 3Ru2Ir（PR3）（mu-H）（4）]（R = Me，3a; Et，3b; Ph，3c; OMe，3d），其中膦以末端方式结合到Ru原子之一上。用PPh2H处理1仅产生一个mu-磷酰基复合物[CP * 3Ru2Ir（mu-PPh2）（mu-H）（3）]（5），其中磷基配体通过中间mu桥接Ru-Ir边缘-磷酸酯络合物[CP * 3Ru2Ir（mu-PPh2）（mu-H）（5）]（6），其中磷酸酯配体桥接Ru-Ru边缘。通过VT-H-1 NMR和选择性脉冲辐射阐明了5中的mu-磷酸配体的通量行为。 5的热解通过PC（ipso）键裂解和还原还原消除了mu（3）-次亚膦配合物[Cp * 3Ru2Ir（mu（3）-PPh）（mu-H）（2）]（7）。苯。

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《Organometallics》 |2009年第3期|共11页
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Shima T; Sugimura Y; Suzuki H;
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H BOND ACTIVATION; DINUCLEAR; ETHYLENE; EXCHANGE; HYDRIDE; IRIDIUM; CLUSTER; DERIVATIVES; KINETICS; LIGAND;

机译：H键活化;核糖;乙烯;交换;氢化物;铱;团簇;衍生物;动力学;配体;

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1. Heterometallic Trinuclear Polyhydrido Complexes Containing Ruthenium and a Group 9 Metal, [CP*3Ru2M(mu(3)-H)(mu-H)(3)] (M = Ir or Rh; Cp* = eta(5)-C5Me5): Synthesis, Structure, and Site Selectivity in Reactions with Phosphines [J] . Shima T, Sugimura Y, Suzuki H Organometallics . 2009,第3期

机译：含有钌和9族金属[CP * 3Ru2M（mu（3）-H）（mu-H）（3）]的杂金属三核多氢配合物（M = Ir或Rh; Cp * = eta（5）-C5Me5）：与膦反应的合成，结构和位点选择性
2. Synthesis, Structures, and Reactivity of Single and Double Cyclometalated Complexes Formed by Reactions of [Cp*MCl₂]₂ (M = Ir and Rh) with Dinaphthyl Phosphines [J] . Shaowei Zhang, Xiaodan Chu, Tongyu Li, ACS Omega . 2018,第4期

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3. Synthesis,Structure and Reactivity of Homo- and Heterobimetallic Complexes of the General Formula [Cp*Ru(mu-Cl)_3ML] [LM = (arene)Ru,Cp*Rh,Cp*Ir] [J] . Laurent Quebatte, Rosario Scopelliti, Kay Severin European journal of inorganic chemistry . 2006,第1期

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4. Synthesis and Structures of Novel Early-Late Heterometallic Polyhydrido Complexes with Cyclopentadienyl Ligands [C] . Yasumasa Takenaka, Jens Baldamus, Zhaomin Hou Symposium on Organometallic Chemistry . 2004

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5. Preparation of sterically hindered bis(secondary phosphines): Structure-selectivity relationships in platinum-catalyzed asymmetric phosphination and synthesis and structure of metal-phosphido complexes [D] . Chapp, Timothy W. 2010

机译：位阻双（仲膦）的制备：铂催化的不对称磷化反应中的结构-选择性关系以及金属-磷化物配合物的合成和结构
6. Synthesis Structures and Reactivity of Single andDouble Cyclometalated Complexes Formed by Reactions of Cp*MCl22 (M = Ir and Rh) with Dinaphthyl Phosphines [O] . Shaowei Zhang, Xiaodan Chu, Tongyu Li, 2018

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8. Chemistry of the Metal Carbonyls. Part 77. Some Reactions of the Platinumtriosmium Complexes (Os3Pt(mu-H)2(CO)10(PR3)) with Donor Molecules; X-Ray Crystal Structures of (Os3Pt(mu-H)2(CO)10(PPh3)2) and (OsPt2(CO)5(PPh3)(mu3-MeC2Me) [R] . Farrugia, L. J., Howard, J. A. K., Mitrprachachon, P., 1980

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Heterometallic Trinuclear Polyhydrido Complexes Containing Ruthenium and a Group 9 Metal, [CP*3Ru2M(mu(3)-H)(mu-H)(3)] (M = Ir or Rh; Cp* = eta(5)-C5Me5): Synthesis, Structure, and Site Selectivity in Reactions with Phosphines

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Heterometallic Trinuclear Polyhydrido Complexes Containing Ruthenium and a Group 9 Metal, [CP3Ru2M(mu(3)-H)(mu-H)(3)] (M = Ir or Rh; Cp = eta(5)-C5Me5): Synthesis, Structure, and Site Selectivity in Reactions with Phosphines